Method for simultaneous extraction of essential oils and antioxidants from labiatae species and the extract products thereof

ABSTRACT

An increase in specific antioxidant activity of extracts from rosemary ( Rosemarinus officinalis ) is obtained by the use of a blend of tetrafluoroethane and acetone in the extraction process. A blend of tetrafluoroethane, acetone and methanol improves total yield. A tetrafluoroethane and acetone blend has higher efficacy but comparatively lower yields. The methods yield a liquid and oily antioxidant extract that is readily mixed with a liquid product such as soybean oil for addition to animal feeds and human food. The methods simultaneously yield pharmaceutical grade essential oils in high yields.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The invention relates generally to a method for simultaneousextraction of essential oils and antioxidants from organic material,more particularly organic material from the Lamiaceae (or Labiatae)family, including rosemary (Rosemarinus officinalis) and, morespecifically, to a method of simultaneous extraction of essential oilsand antioxidants from species of the family Labiatae, in particular,rosemary, using solvent blends and which yields a liquid, oily extractcontaining antioxidants and a liquid extract containing essential oils.The extract containing antioxidants is readily mixed with an edible oilfor addition to animal feeds and human food. The essential oils arepharmaceutical grade.

[0003] 2. Background of the Prior Art

[0004] Worldwide demand for natural antioxidants has been rising due tosafety concerns about synthetic food and feed additives and the publicperception that natural food and feed supplements provide certain healthbenefits. The most important natural antioxidants being exploitedcommercially today are tocopherols. Tocopherols have a potent ability toinhibit lipid peroxidation in vivo by trapping peroxy-radicals (Burton,G. W., and K. U. Ingold (1989), in Vitamin E: Biochemistry and HealthImplications, edited by A. T. Diplock, L. J. Machlin, L. Packer and W.A. Pryor, The New York Academy of Sciences, New York, pp. 7-22). Variousherbal extracts for use as natural antioxidants are being explored.Possibilities include the extraction of rosemary or other botanicalsources. Such new antioxidants may play a role in combatingcarcinogenesis as well as the aging process, and may be applicable inthe nutraceutical industry.

[0005] Among the various natural extracts available in the market arerosemary extracts, which are reported to be highly effective inretarding lipid oxidation and protecting living cells from the damagingoxidative stress (Chen, Q., H. Shi and C-T Ho (1992), “Effects ofrosemary extracts and major constituents on lipid oxidation and soybeanlipoxygenase activity”, J Am Oil Chem Soc 69: 999-1002; Wong, J. W., K.Hashimoto and T. Shibamoto (1995), “Antioxidant activities of rosemaryand sage extracts and vitamin E in a model meat system”, J Agric FoodChem 43: 2707-2712). These extracts are described as being superior tovitamin E, a well-known natural antioxidant and food supplement, in manyfood model systems (Lolinge, J. (1983), Natural antioxidants in Allen,J. C. and R. J. Hamilton eds, Rancidity in Foods, Elsevier AppliedScience, London, Chapter 6). However, opposite findings are alsodocumented. Wong et al. (1995) revealed that vitamin E is more effectivethan rosemary extract in a cooked beef homogenate. Additionally,rosemary extract is shown to be a synergist of vitamin E in stabilizingor retarding oxidation in sardine oil and fish muscle (Fang, X. and S.Wanda (1993), “Enhancing the antioxidant effect of α-tocopherol withrosemary extract in inhibiting catalyzed oxidation caused by Fe²⁺ andhemoprotein”, Food Res Int 26: 405-411; Wanda, S. and X. Fang (1992),“The synergistic antioxidant effect of rosemary extract and α-tocopherolin sardine oil model system and frozen-crushed fish meat”, J FoodProcess Preserv 16: 263-274).

[0006] As to the extraction of rosemary, many authors report that polarsolvents yield extracts with higher antioxidant activities (Chang, S.S., B. Ostric-Matijasevic, C-L Huang and OA-L Hsieh (1977), “Naturalantioxidants from rosemary and sage”, J Food Sci 42: 1102-1106). Chen etal. (1992) found that hexane extracts of rosemary contained a highercontent of carnosic acid and carnosol than methanol extracts do.Carnosic acid and carnosol are the effective antioxidant molecules inrosemary. Carnosic acid and carnosol have been suggested to account forover 90% of the antioxidant activity of rosemary extracts (Aruoma, I. I,B. Halliwell, R. Aeschbach and J. Loligers (1992) “Antioxidant andpro-oxidant properties of active rosemary constituents: carnosol andcarnosic acid”, Xenobiotica 22: 257-268). Antioxidant molecules ingeneral, and rosemary antioxidants specifically, are by nature labilemolecules especially when exposed to heat and/or air. During theharvest, the drying, and the regular solvent extraction of rosemary,some oxidation is likely to occur. Through a process of chemicalreactions, carnosic acid, the naturally-occurring antioxidant moleculein rosemary, is believed to be the precursor to carnosol and many otherantioxidants found therein (Wenkert, E., A. Fuchs, J. D. McChesney(1965), “Chemical artifacts from the family labiate”, J. Org. Chem. 30:2931-2934). It can be demonstrated that the freshly cut leaves ofrosemary do not contain carnosol (Aeschbach, R. and L. Philippossian(1993), “Camosic acid obtention and uses”, U.S. Pat. No. 5,256,700).Carnosic acid is about 10 times more effective as an antioxidant thancarnosol (Aruoma et al., 1992), and it, therefore, is important for thehigh activity of a rosemary extract to minimize the damage to carnosicacid.

[0007] Essential oils are volatile oils which are the aroma and flavorcomponents of organic material. They are used in a variety of productssuch as incense, aromatherapy oils, perfumes, cosmetics,pharmaceuticals, beverages, and foods. The market for these oils demandsconsistent high quality and reliable supplies at competitive prices.Essential oils are typically commercially extracted from organicmaterial such as rosemary using steam distillation. In this prior artprocess, the antioxidants are destroyed, and thermal degeneration of theessential oils may occur.

[0008] The antioxidant activity of commercially available rosemaryproducts was compared with rosemary extracts prepared in the laboratoryusing various solvents for extraction. It was found that the antioxidantactivity of commercial rosemary products was in the range of 2-5% whencompared to mixed tocopherols. A methanol extract had 10% of theactivity of mixed tocopherols. Methanol extraction, moreover, results ina dry powder that is difficult to dissolve into preferred carriers, suchas edible oils. Accordingly, there were identified goals to increase thespecific activity of extracts of species of the family Labiatae,including rosemary, by optimizing the solvent extraction methodology, totest alternate extraction technologies, and to improve the handlingcharacteristics of the extract.

[0009] The investigation into alternate extraction technology had twoprimary objectives. Firstly, to increase the specific activity of therosemary extracts further for more efficient formulation into soybeanoil or other carrier; and, secondly, to identify technology allowing theremoval of the essential oil fraction from the extracted materialwithout oxidative destruction of the carnosic acid. One extractiontechnique investigated is based on tetrafluoroethane (TFE).

[0010] A process for the extraction of antioxidants and essential oilsfrom rosemary preferably meets several criteria. It should be economicaland also lead to a liquid or oil antioxidant extract that can beformulated into a homogeneous, soybean oil-based final product that islargely free of odor.

[0011] For the foregoing reasons, it is desired that a process be foundthat simultaneously yields antioxidants and essential oils suitable forfurther commercial use via a single solvent mix. The present inventionsolves this problem with sufficiently high yields and purities to be acommercially-viable process.

SUMMARY OF THE INVENTION

[0012] This invention is directed to a method of simultaneouslyextracting antioxidants and essential oils from organic materials andthe extract products of the method.

[0013] A purpose of the invention is to identify a solvent blend andextraction parameters for the extraction of antioxidants of rosemarywhile attaining a high specific activity and retaining high extractionyields.

[0014] Another purpose of the present invention is to provide a methodfor extracting antioxidants from rosemary that yields a liquid, oilyextract that is readily mixed with a liquid product, such as soybeanoil, for incorporation into animal feeds and human foods.

[0015] A further purpose of the present invention is to provide a methodfor extracting essential oils from rosemary in high yields and highpurity.

[0016] The organic material used during testing was dried, finely groundrosemary of the Arp variety. It is anticipated that the organic materialcan be any plant of the Labiatae family, and more broadly, any plantmaterial which contains antioxidants and essential oils. It is alsoexpected that any parts of the plant which contain the desiredcomponents may be extracted, as well as any form of the plant material(e.g., whole, ground, fresh, or dried).

[0017] Tetrafluoroethane was used in the solvent blend.Tetrafluoroethane has a boiling point of −27° C. The technology utilizesthe vapor pressure of the solvent at room temperature and allowsextraction under mild conditions, therefore minimizing the oxidativedecomposition of carnosic acid during the extraction process.Tetrafluoroethane is substantially apolar and is preferably blended withacetone in the extractions of rosemary described here. The advantages ofTFE show that it is non-flammable, has a low boiling point, isenvironmentally acceptable (very low toxicity), and is easily handled.It has been found that at ambient or sub-ambient temperatures, TFEleaves behind the majority of the waxes and other non-fragrant materialsnormally extracted with conventional solvents (Wilde P. F., 1994.Fragrance Extraction. European Patent No. 0616821A1). Another advantagewith the use of TFE is that no distillation must be employed due to itslow boiling point. It is anticipated that any hydrofluorocarbon (HFC)with a hydrocarbon backbone of three carbons or fewer (C1-C3) may beused, or mixtures thereof. Acetone and methanol were the organicsolvents in the solvent blend. Though methanol alone extracts theantioxidants from rosemary very effectively, it leads to a dry powderextract and an inferior liquid final product after formulation intosoybean oil. The optimum TFE-based solvent blend for the extraction ofantioxidants from rosemary was identified and extraction parameters weredefined. Among numerous solvent blends tested, an 80/15/5 weight percentblend of TFE/methanol/acetone, respectively, proved to be the mosteffective solvent resulting in a liquid extract with up to 35% of thetocopherol efficacy and an antioxidant yield of about 60% of therosemary antioxidants. Mixtures of TFE and hexane or butane have beentested as well. Though hexane or butane works, they are not as efficientas acetone and methanol. It is anticipated that similar individualorganic solvents added to the TFE may be used as well, or mixturesthereof. Examples include, but are not limited to, ethanol, ethylenechloride, isopropanol, methylene chloride, propylene glycol, and otherfood grade solvents. Yields may differ with different solvent mixtures,but any similar solvent mixture should simultaneously yield essentialoils and antioxidants using the present process.

[0018] The organic material and solvent blend are added together in a1:3 (organic material:solvent blend) or higher (i.e., 1:4, 1:5, etc.)weight ratio to perform the extraction step in any vessel which will becompatible with the components. Since the TFE is preferably added inliquid form, the vessel has to be a pressure vessel which will withstandpressures equal to those required to maintain the TFE in liquid form.The extraction has been carried out at ambient temperatures, but thepressure and temperature may be varied, so long as the TFE and organicsolvents remain in liquid form. The extraction appears to be almostinstantaneous when dried, finely ground rosemary is used, as there wasno appreciable difference in efficacy of products and only smalldifferences in yield whether the extraction is done for 5 minutes or 2hours. The extraction has been carried out at greater than ambienttemperature (up to approximately 40° C.) and found to increase yields(e.g., 7-8% crude extract at standard temperature and pressure and 17%crude extract at 40° C.) with a decline in efficacy of the products anda change in the physical characteristics of the final product due towhat is believed to be an increased extraction of longer chainhydrocarbons.

[0019] The method for removing the organic material from the solutionwas filtration. Any suitable separation process known to one skilled inthe art which does not interfere with the other steps of the method maybe used.

[0020] The removal of the solvent blend has been accomplished byevaporation. Specifically, the removal has been in steps in order toremove the solvents selectively. The TFE may be removed by any suitablemethod known to one skilled in the art. A thin film evaporator isanticipated to be suitable for this process. The organic solvent(s) maybe removed by any suitable method known to one skilled in the art aswell. A wipe film evaporator is anticipated to be suitable for thisprocess.

[0021] Once the TFE is removed, it may be cooled or the pressureincreased until it reaches its liquid phase and recycled back for reuse.Removal of the organic solvent(s) in the wipe film evaporator yields theoily, liquid antioxidants. The organic solvent(s) may be further treatedby any suitable process known to one skilled in the art, specificallycolumn distillation, to separate the organic solvent(s) from theessential oils. The resulting essential oils are of very high purity(pharmaceutical grade) and surprisingly high yields (compared toprevious extraction methods for obtaining essential oils).

BRIEF DESCRIPTION OF THE DRAWINGS

[0022]FIG. 1 is a process diagram of the preferred embodiment of theextraction method of the present invention.

[0023]FIG. 2 is a chart of the antioxidant efficacy of a number ofsamples of rosemary extracted according to described Method 1.

[0024]FIG. 3 is a chart of the antioxidant efficacy of a number ofsamples of rosemary extracted according to described Method 1.

[0025]FIG. 4 is a chart of the antioxidant efficacy of a number ofsamples of rosemary extracted according to described Method 1.

[0026]FIG. 5 is a chart of the antioxidant efficacy of a number ofsamples of rosemary extracted according to described Method 1.

[0027]FIG. 6 is a chart of the antioxidant efficacy of a number ofsamples of rosemary extracted according to described Method 1.

[0028]FIG. 7 is a chart of the antioxidant efficacy of a number ofsamples of rosemary extracted according to described Method 2.

[0029]FIG. 8 is a chart of the antioxidant efficacy of a number ofsamples of rosemary extracted according to described Method 3.

[0030]FIG. 9 is a chart of the antioxidant efficacy of a number ofsamples of rosemary extracted according to described Method 4.

[0031]FIG. 10 is a schematic diagram of extraction Method 1 of thepresent invention.

[0032]FIG. 11 is a schematic diagram of extraction Method 2 of thepresent invention.

[0033]FIG. 12 is a schematic diagram of extraction Method 3 of thepresent invention.

[0034]FIG. 13 is a schematic diagram of extraction Method 4 of thepresent invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0035] The preferred embodiment of the method of the present inventionis shown in FIG. 1. The process includes an extraction vessel 10 wherethe organic material 12 is extracted using the solvent blend at apressure equal to that necessary to keep the TFE in liquid form and atambient temperature. The solvent blend is premixed in a solvent blendtank 14 before being added to the extraction vessel 10 where the organicmaterial 12 has been added. The solvents are added to the solvent blendtank 14 from fresh supply tanks, acetone tank 16, methanol tank 18, andTFE tank 20, or alternatively, recycled from the end separationtechniques.

[0036] After the desired natural organic components are extracted fromthe organic material 12 after a sufficient residence time, the mixtureis passed through a filter 22. The filtered extract then passes througha thin film evaporator 24 where the TFE is removed and the remainingextract passes to the next step. The removed TFE is recycled backthrough a cold-trap 26 to the TFE tank 20 for reuse.

[0037] The TFE-free extract then passes through a wipe film evaporator28 where the liquid, oily antioxidant portion of the extract 30 iscollected and the organic solvent portion of the extract is treatedfurther. The organic solvent portion of the extract passes throughcolumn distillation 32 to separate the essential oils 34 from theorganic solvents. The organic solvents are condensed in a cold-trap 26before being recycled back to the solvent blend tank 14.

[0038] The methods of this invention are further illustrated by thefollowing experimental examples.

EXAMPLES Example 1

[0039] The invention identifies methods of extracting rosemary withdifferent TFE-based solvents and define preferred extraction conditions.A total of 17 different solvent blends, individually and combined, wereused. Data presents the results of the analysis of extracts of rosemaryproduced from the Arp variety in terms of extraction yield (%) andpercent efficacy when compared to 100% mixed tocopherols at equalapplications of 500 ppm tested in chicken fat, and rosemaryextract/tocopherols equivalency.

[0040] All samples were tested in untreated chicken fat at a treatmentlevel of 500 ppm. These samples were then placed into an oxygen bombpressurized to 50 psi with oxygen, placed in silicon oil at 100° C. andallowed to oxidize. All samples were compared against the induction timeof fat treated with 250 ppm 100% mixed tocopherols at a calculated equalconcentration level of 500 ppm.

[0041] In the data tables, the sample number, the solvent used, percentyield, percent efficacy of tocopherols, and equivalency of rosemaryextract to grams of tocopherols are reported. The percent yield wascalculated by dividing the yield of rosemary extract by the initial massof rosemary and multiplication by 100%. The percent efficacy totocopherols was calculated as follows:$\frac{{{IT}_{sample}\left( {500\quad {ppm}} \right)} - {IT}_{control}}{2\left( {{IT}_{{tocopherols250}\quad {ppm}} - {IT}_{control}} \right)} \times 100\quad \%$

[0042] where “IT” is the induction time.

[0043] Tocopherol equivalent units (g) were calculated using theassumptions that 1.0 kg rosemary was extracted according to theindividual methods, and the percent yield and percent efficacy areequivalent from the small scale to the large scale extraction process:

1000 g rosemary×(% yield/100%)×(% efficacy/100%)=tocopherol equivalent(g).

[0044] The poultry fat, used as a test matrix, was supplied from Tyson.The various rosemary accessions were obtained from the Chart Co., PapaGeno's Herb Garden, and the North Carolina Botanical Garden. Allsolvents were purchased from Fisher Scientific Co. The apparatus thatthe TFE/organic experiments were conducted in was purchased from theAdvanced Phytonics facility in Cowfold Grange, Leeming, U.K. Allrosemary leaves used in these experiments were from the Arp varietyunless otherwise noted.

Method 1 Effect of Solvent Blends on Efficacy

[0045] For samples 1-17, 2.0 g of dried, ground rosemary leaves wereintroduced into a closed glass vial extractor. The sample was thenextracted with 20 g tetrafluoroethane (TFE) or a TFE/solvent mix for twohours. At this time the filtrate was quantitatively transferred into aglass collection vial. The rosemary was then washed with 10.0 g of theextraction solution for five minutes. This liquid portion was added tothe first filtrate collected. The rosemary was washed a second time with10.0 g of the extracting solution and this was also added to thecollection vial. After all of the filtrate solutions had been combined,the pressure in the vial was slowly released. After all of the TFE hadevaporated, the other organic solution was removed under a stream ofnitrogen gas under moderate heating. The extraction process isillustrated diagrammatically in FIG. 10.

[0046] The purpose of this series of experiments (FIG. 2, samples 1-7)was to test the performance of various TFE/acetone blends for theextraction of antioxidants from rosemary. When used alone, TFE resultsin poor yield with low efficacy. Acetone was added in small amounts tothe TFE, initially at a concentration of 5%. The efficacy of theextracts was increased dramatically, up to six-fold, when sample number2 (95% TFE/5% acetone) was compared to the efficacy of the sample number1 (100% TFE). As the concentration of the acetone was increased, yieldsincreased steadily while the specific efficacy remained essentially thesame after an initial steep increase. It appears that with increasingconcentrations of acetone, the blend equally well extracts antioxidantcomponents as well as non-antioxidant components. The yield data arepresented in Table 1 and the antioxidant efficacy is illustrated in FIG.2. TABLE 1 Tocopherol % Efficacy Equivalent No. Solvent % Yield toTocopherols Units (g) 1 100% TFE 0.95  5.84 0.555 2  95% TFE/5% acetone3.27 35.71 11.7 3  90% TFE/10% acetone 5.06 37.01 18.7 4  85% TFE/15%acetone 6.50 35.71 23.21 5  80% TFE/20% acetone 6.11 34.41 21.0 6  75%TFE/25% acetone 6.54 34.41 22.5 7  70% TFE/30% acetone 7.49 27.92 20.9

[0047] The purpose of the next set of experiments (FIG. 3, samples 1,8-13) was to test the effect of varying the concentration of hexane whenmixed with TFE. Generally, the effect of hexane added to TFE had a lesspronounced effect on the performance when compared to the acetoneresults. However, as was observed with the acetone, hexane was also ableto improve the efficacy of the extracts by five-fold when compared tosample number 1 (100% TFE). The yield data are presented in Table 2 andthe antioxidant efficacy is illustrated in FIG. 3. TABLE 2 Tocopherol %Efficacy Equivalent No. Solvent % Yield to Tocopherols Units (g)  1 100%TFE 0.95  5.84 0.555  8  95% TFE/5% hexane 1.90 24.02 4.6  9  90%TFE/10% hexane 2.79 24.02 6.7 10  85% TFE/15% hexane 4.85 24.02 11.6 11 80% TFE/20% hexane 5.69 24.02 13.7 12  75% TFE/25% hexane 5.46 26.6214.53 13  70% TFE/30% hexane 6.40 26.62 17.0

[0048]FIGS. 4 and 5 (samples 2-13) compare the two different groups ofsolvent systems in terms of yields and specific activity. A steadyincrease in extraction yields can be noted as the TFE is replaced by thetwo solvents hexane or acetone. As to the specific activity, a rapidincrease followed by a long plateau is observed. On average theTFE/acetone extracts outperformed the TFE/hexane extracts by about 10%in terms of specific activity. However, at a concentration of 30% forboth solvents, the extracts were approximately equal in efficacy.

[0049] Additional solvents and solvent mixes were tested in an attemptto increase the efficacy and the total antioxidant yield extracted fromthe rosemary. Table 5 and FIG. 6 (samples 1 and 14-17) display theresults of these experiments. When a 90% TFE/10% butane blend wasevaluated a three-fold increase in efficacy over sample number 1 (100%TFE) was observed. The TFE/butane extract was equal to a methanolextract. Next, several three-solvent blends were tested. The twosolvents mixed with TFE were methanol and acetone, varying inconcentration from 5 to 15 percent (see Table 4). Using a solvent mix of80% TFE/15% MeOH/5% acetone, the extract obtained displayed the highesttotal yield with a specific efficacy of 29.22% of that of tocopherol andan extraction yield of 10.05%. Methanol in combination with acetoneseems to augment extraction yields while maintaining high specificefficacy. The yield data are presented in Table 3 and the antioxidantefficacy is illustrated in FIG. 6. TABLE 3 Tocopherol % EfficacyEquivalent No. Solvent % Yield to Tocopherols Units (g)  1 100% TFE 0.95 5.84 0.555 14  90% TFE/10% butane NA 20.12 — 15  80% TFE/5% MeOH/ 7.8530.52 23.9  15% acetone 16  80% TFE/10% MeOH/ 6.34 34.42 21.8  10%acetone 17  80% TFE/15% MeOH/ 10.05  29.22 29.4  5% acetone

Method 2 Effect of Multiple Extractions on Efficacy and Yield

[0050] For sample 18, 2.0 g of dried ground rosemary leaves wereintroduced into the glass-extracting vial. The sample was then extractedwith 20.0 g of 85% TFE/15% acetone for two hours. This was repeated oncemore. At this time 40.0 g of the solvent mix was added to the extractionvial containing the rosemary. This was allowed to stand for 20 hours.The solvent was then removed and added to the previous two extracts. TheTFE was then allowed to evaporate off and the acetone was removed undera stream of nitrogen gas with slight heat. The process is illustrateddiagrammatically in FIG. 11.

[0051] The possibility of attaining higher yields with repeatedextractions while retaining the high efficacy of the extracts wasexplored. FIG. 7 represents the antioxidant activity of sample 18.Sample 18 was produced from the repeated extraction of rosemary over a24-hour period using 85% TFE/15% acetone. No appreciable increase in theyield or decrease in efficacy was observed when compared to a singleextraction. Table 4 presents the yield data. TABLE 4 Tocopherol %Efficacy Equivalent No. Solvent % Yield to Tocopherols Units (g) 18 85%TFE/15% acetone 6.70 33.12 22.2

Method 3 Effect of Extracting a Methanol Extract of Rosemary with a TFEBlend

[0052] Sample 19 was prepared by taking 100.0 g of Arp rosemary leavesand extracting it with 600 ml of methanol for 48 hours. This was thenfiltered and the methanol was evaporated via vacuum rotary evaporator at40° C. Samples 20 and 22 were prepared by taking 1.0 g of sample 19 andputting it into a glass-extracting vial. For sample 20, 10 g of 85%TFE/15% acetone was added to the 1.0 g of sample 19. This solution wasallowed to extract the 1.0 g sample for two hours. This solution wasthen filtered away from the sample. This was repeated once more. Bothsolutions were then combined, the TFE was allowed to boil off, and theacetone was removed under a stream of nitrogen gas with slight heat. Forsample 22, the same method was followed to prepare sample 20, however,instead of using 85% TFE/15% acetone as the extracting solvent, 70%TFE/30% hexane was used. The material (bagasse) that was left over fromthe process of preparing samples 20 and 22 was labeled 21 and 23,respectively. This process is illustrated schematically in FIG. 12.

[0053] The possibility of utilizing the TFE based extraction process tofurther deodorize and purify a methanol extract of rosemary was explored(see FIG. 8). Methanol extracts possess close to 100% of theantioxidants from rosemary. With this in mind, TFE mixed with an organicsolvent (acetone or hexane) may separate out or extract a largermajority of the antioxidants from a methanol extract over dried, groundrosemary leaves. The test was performed with both, acetone and hexane.Initial tests indicated that the TFE blend solvent extracts wereapproximately equal to the methanol extracts of dried, ground rosemary.The non-extracted portion, the bagasse, left over from the TFE basedextraction (samples 21 and 23), retained a large amount of theantioxidant activity which had 13.64% and 12.34%, respectively, of thetocopherol activity. This residual efficacy indicated the lack ofability of the TFE/organic solvent mix to extract 100% of theantioxidants from a methanol extract of rosemary. Table 5 presents theyield data and FIG. 8 displays the antioxidant efficacy. TABLE 5Tocopherol % Efficacy Equivalent No. Solvent % Yield to TocopherolsUnits (g) 19 100% methanol 27.66 20.13 36.0 20  85% TFE/15% acetone 3.91 38.31 15.0 21 Residue NA 13.64 — 22  70% TFE/30% hexane  6.0633.12 20.1 23 Residue NA 12.34 —

Method 4 Extraction of Rosemary with 90% TFE/10% Acetone Followed byExtraction of the Bagasse with Methanol

[0054] Sample 24 was prepared by taking 15.0 g of ground rosemary andplacing it into a 250 ml-extracting vial. To this was added 100.0 g of a90% TFE/10% acetone solvent mixture. This was allowed to stand for twohours and then the solvent was filtered away. The TFE was allowed toboil away and the acetone was removed under a stream of nitrogen gaswith slight heat. The remaining bagasse was used to create sample 25.Sample 25 was prepared in the following way. Firstly, the remainingunextracted rosemary left over from the preparation of sample 24 was putinto a 250 ml flask and 60 ml of methanol was added. This was allowed toextract for 48 hours. At this point, the solution was filtered and themethanol was removed via vacuum rotary evaporator at 40° C. This processis illustrated diagrammatically in FIG. 13.

[0055] Whether any residual antioxidants are left after an extractionwith a TFE blend was investigated (see FIG. 9). A sample of rosemary wasextracted with a 90% TFE/10% acetone (sample 24) mix and the residualrosemary material was extracted with methanol (sample 25). The resultsindicated that a blend of TFE/10% acetone extracted approximately 30% ofthe antioxidants in rosemary. It appears that the presence of methanolin the solvent blend for the extraction of rosemary is critical foreconomical yields. The yield data are presented in Table 6 and theantioxidant efficacy displayed in FIG. 9. TABLE 6 Tocopherol % EfficacyEquivalent No. Solvent % Yield to Tocopherols Units (g) 24  90% TFE/10%acetone 4.00 31.82 12.7  25 100% methanol 23.7 12.34 29.24

Example 2 Essential Oils Analysis

[0056] A sample of 1.8 kg of dried, finely ground rosemary was extractedfor 1 hour at a temperature of 25-26° C. at a pressure of 7 bar using 18kg of a solvent blend of 80% TFE, 12% methanol, and 8% acetone. Afterremoval of the TFE, the extract was subjected to distillation to pulloff the acetone and methanol. Analysis of the distillate by gaschromatography followed by mass spectroscopy showed the presence of theessential oils α-pinene, camphene, β-pinene, β-myrcene, eucalyptol,camphor, and caryophyllene.

[0057] Although the invention has been described with respect to apreferred embodiment thereof, it is to be also understood that it is notto be so limited since changes and modifications can be made thereinwhich are within the full intended scope of this invention as defined bythe appended claims.

We claim:
 1. A process for simultaneously extracting at least a firstand a second natural organic component from organic material, comprisingthe steps of: (a) contacting the organic material in a vessel with ablend of solvents to simultaneously extract the natural organiccomponents into the solvent blend; (b) removing the remaining organicmaterial from the solution of the natural organic components and thesolvent blend; and (c) removing the solvent blend to isolate theproducts containing the first and second natural organic components. 2.The process of claim 1, wherein the blend of solvents contains at leastone C1-C3 HFC and at least one organic solvent.
 3. The process of claim2, wherein the HFC is tetrafluoroethane.
 4. The process of claim 3,wherein the organic solvent is selected from the group consisting ofacetone, methanol, butane, and hexane.
 5. The process of claim 3,wherein the solvent blend comprises from between about 60% to about 95%tetrafluoroethane.
 6. The process of claim 5, wherein the solvent blendcomprises tetrafluoroethane and at least two organic solvents.
 7. Theprocess of claim 6, wherein the organic solvents are selected from thegroup including acetone, methanol, butane, and hexane.
 8. The process ofclaim 7, wherein the solvent blend comprises between about 70% and about85% tetrafluoroethane, between about 1% and about 25% acetone, andbetween about 1% and about 25% methanol.
 9. The process of claim 5,wherein the solvent blend comprises between about 70% and about 95%tetrafluoroethane and the organic solvent is acetone.
 10. The process ofclaim 5, wherein the solvent blend comprises between about 70% and about90% tetrafluoroethane and the organic solvent is methanol.
 11. Theprocess of claim 5, wherein the solvent blend comprises between about70% and about 90% tetrafluoroethane and the organic solvent is hexane.12. The process of claim 1, wherein the first natural organic componentcomprises an antioxidant.
 13. The process of claim 12, wherein the firstnatural organic component comprises organic molecules having polaritycomparable to antioxidants.
 14. The process of claim 1, wherein thesecond natural organic component comprises essential oils.
 15. Theprocess of claim 3, wherein the step of removing the solvent blendcomprises the steps of: (a) evaporating the tetrafluoroethane, (b)evaporating the organic solvent(s), and (c) distilling the organicsolvent(s).
 16. The process of claim 15, wherein the step of evaporatingthe tetrafluoroethane is accomplished via thin film evaporation.
 17. Theprocess of claim 15, wherein the step of evaporating the organicsolvent(s) is accomplished via wipe film evaporation.
 18. The process ofclaim 15, wherein the step of distilling the organic solvent(s) isaccomplished via column distillation.
 19. A process for extractingmolecules having polarity comparable to antioxidants and essential oilsfrom botanical material, comprising the steps of: (a) contacting thebotanical material in a vessel with a blend of tetrafluoroethane and atleast one organic solvent to simultaneously dissolve the molecules andthe essential oils in the solvent blend; (b) removing the remainingbotanical material from the solution of the molecules, the essentialoils, and the solvent blend; and (c) removing the solvent blend toisolate a liquid, oily product containing the molecules and essentialoils and a liquid containing the essential oils.
 20. A process forsimultaneously extracting at least a first and a second natural organiccomponent from botanical material, comprising the steps of: (a)contacting the botanical material in a vessel with a blend oftetrafluoroethane and at least one organic solvent to simultaneouslydissolve the first and the second natural organic components in thesolvent blend; (b) removing the remaining botanical material from thesolution of the first natural organic component, the second naturalorganic component, and the solvent blend; and (c) removing the solventblend to isolate a liquid, oily product containing the first naturalorganic component which has antioxidant activity and a liquid productcontaining the second natural organic component which contains essentialoils wherein the natural organic components are improved over naturalcomponents extracted in the absence of the organic solvent.
 21. Theprocess of claim 20, wherein the liquid, oil product containing thefirst natural organic component is readily soluble in an edible oil. 22.The process of claim 20, wherein the botanical material is a member ofthe family Labiatae.
 23. The process of claim 22, wherein the member ofthe family Labiatae is Rosemarinus officinalis.
 24. A preservative forfoods and animal feedstuffs, comprising a mixture of the liquid, oilyproduct obtained from the process of claim 20 and an edible oil.
 25. Anorally administered antioxidant for humans and animals, comprising amixture of the liquid, oily product obtained from the process of claim20 and an edible carrier.
 26. An essential oil product comprising theliquid product containing the essential oils obtained from the processof claim 20.